Polymers comprising benzotriazole for use in optical devices

ABSTRACT

The present invention relates to polymers comprising benzotriazole containing repeating units. Optical devices, comprising the polymers of the present invention, can show significant advantages in color purity, device efficiency and/or operational lifetime. In addition, the polymers can have good solubility characteristics and relatively high glass transition temperatures, which facilitates their fabrication into coatings and films that are relatively thin, thermally stable, and relatively free of defects.

The present invention relates to novel polymers comprising benzotriazolcontaining repeating units and to their use in optical devices, such asan optical device comprising an electroluminescent device or aphotovoltaic device.

Derivatives of poly(p-phenylenevinylene) have been known for some timeas electroluminescence (EL) materials (see, for example, WO90/13148).

WO98/11150 discloses triazine polymers of formula

and their use in electroluminescence (EL) arrangements.

WO00/46321 and U.S. Pat. No. 6,512,083 relate to fluorene-containingpolymers and their use in EL arrangements.

WO01/49768 discloses luminescent polymers comprising a triarylene repeatunit which comprises a triarylene of general formula

which is substituted or unsubstituted and an arylene repeat unit—[—Ar—]— that is different from the triarylene repeat unit wherein X″and Y″ are each independently O, S, CR, SiR or NR and each R isindependently alkyl, aryl or H.

WO97/12882 relates to benzotriazole polymers having general formula

which are useful as ultraviolet light stabilizers and metal chelaters.The products of WO97/12882 are derivatives of 4-hydroxyacetophenonebenzotriazole and 4-hydroxyphenylmethyl carbinol benzotriazole.

WO02/059121 relates to monomers having general formula

which may be substituted or unsubstituted: where X′ and Y′ are the sameor different and are reactive groups capable of undergoing chainextension; X is O, S, NR, RC—CR or RC═CR; Y is O, S, NR, RC—CR or RC═CR;R is H or a substituent group; and Ar is a substituted or unsubstitutedaryl or heteroaryl group.

There are a number of challenges faced with the introduction of organicEL displays when their performance is compared with existingtechnologies. Obtaining the exact color coordinates required by specificguidelines (i.e. NTSC) has been problematic. The operational lifetime ofthe EL device is relatively lower when contrasted to the existinginorganic technology. In addition, producing a material with a pure bluecolor and a long lifetime is one of the greatest problems for thisindustry.

Accordingly, it is the object of the present invention to provide novelmaterials, which show significant advantages in color purity, deviceefficiency and/or operational lifetime, when incorporated in opticaldevices.

Said object is solved by the polymers of the present inventioncomprising benzotriazole containing repeating units. Optical devices,comprising the polymers of the present invention, can show significantadvantages in color purity, device efficiency and/or operationallifetime. In addition, the polymers can have good solubilitycharacteristics and relatively high glass transition temperatures, whichfacilitates their fabrication into coatings and films that arerelatively thin, thermally stable, and relatively tree of defects. Ifthe polymers contain end groups which are capable of being crosslinked,the crosslinking of such groups after the films or coating is formedincreases the solvent resistance thereof, which is beneficial inapplications wherein one or more solvent-based layers of material aredeposited thereon.

Accordingly, the polymers of the present invention should have a glasstransition temperature above 100° C., especially a glass transitiontemperature above 150° C.

The repeating units of the polymers of the present invention comprise abenzotriazole backbone

wherein the phenyl group of the benzotriazole may be substituted in anypattern, including fused ring systems. The benzotriazole monomer (orcomonomer) may give rise to a main-chain or a pendant structure of thepolymer, both of which may be conjugated or non-conjugated. The presentinvention is not limited to a benzotriazole structure where oneconnection to the polymer is through the phenyl ring or a group attachedthereto and the other is through the substituent attached to thenitrogen atom. Other structures may exist where both links to thepolymer chain are on the phenyl ring or a group attached thereto, andsimilarly, where both polymer connections are on the substituentattached to the nitrogen atom. In addition, the benzotriazole moiety maybe connected to a polymer in a pendant manner.

Examples of the benzotriazole backbones are groups of the followingformula

wherein A²¹, A²², A²³, A²⁴, A¹¹, A¹², A¹³, A¹⁴′, A¹⁵, A¹⁶, A¹⁷ and A¹⁸are independently of each other H, halogen, SO₃ ⁻, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or —CO—R²⁸,wherein E, D, G and R²⁸ are defined as below, ortwo groups A¹¹, A¹², A¹³, A¹⁴′, A¹⁵, A¹⁶, A¹⁷ and A¹⁸, which areneighbouring to each other, are a group

wherein A³¹, A³², A³³, A³⁴, A³⁵, A³⁶ and A³⁷ are independently of eachother H, halogen, SO₃ ⁻, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby E and/or interrupted by D, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —CO—R²⁸, and up to 2 substituents A²¹, A²², A²³, A²⁴,A¹¹, A¹², A¹³, A¹⁴′, A¹⁵′, A¹⁶, A¹⁷, A¹⁸, A³¹, A³², A³³, A³⁴, A³⁵, A³⁶and A³⁷ can represent the connection to the polymer.

As used herein the term “polymer of the present invention” refers topolymers having repeating units of formula I, including formula Ia toId, II, including formula IIa to IIg, formula III, and/or formula IV,including formula IVa to IVc.

Accordingly, the present invention relates to polymers comprising arepeating unit of the formula

x and y are 0 or 1,X¹ and X² are independently of each other a divalent linking group,Ar¹, Ar², Ar³, Ar⁴, Ar⁵, A⁶, Ar⁷ and A⁸ are independently of each otheran aryl group, or a heteroaryl group, which can optionally besubstituted, especially a C₆-C₃₀aryl group, or a C₂-C₂₆heteroaryl group,which can optionally be substituted.

In the repeating units of formula IV at least one of x and y is 1. If xand y are both 1, repeating units of formula

results, which could be seen as a “crosslinking structure”, present in0.01-3%. Preferred are, however, repeating units of formula

Among the repeating units of the formula I, repeating units of formula

are preferred, wherein Ar² is as defined above,R¹ and R² are independently of each other H, halogen, SO₃ ⁻,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or —CO—R²⁸,or two substituents R¹ and R², which are adjacent to each other, are agroup

D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; —OCOOR²⁷;or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; orR²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—,R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Preferably, R¹ and R² are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, orsec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl.

D is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵is C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, orbiphenyl.

E is preferably —OR²⁹; —SR²⁹; —NR²⁵R²⁵; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁵; or—CN; wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each otherC₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₂₄aryl, suchas phenyl, naphthyl, or biphenyl.

Examples of Ar² are a single bond, —CO—, —COO—; —S—; —SO—; —SO₂—; —O—;—CR²³═CR²⁴—; or —

n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1to 3,R⁶ and R⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —CO—R²⁸, R⁸ is C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, or C₇-C₂₅aralkyl,R⁹ and R¹⁰ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl, orR⁹ and R¹⁰ form a ring, especially a five- or six-membered ring,R^(14′) and R^(15′) are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G,D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; —OCOOR²⁷;or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; orR²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Preferably, R⁶ and R⁷ are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl,2-ethylhexyl, or n-heptyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, such as —CH₂OCH₃, —CH₂OCH₂CH₃, —CH₂OCH₂CH₂OCH₃, or—CH₂OCH₂CH₂OCH₂CH₃, C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl,C₆-C₂₄aryl which is substituted by G, such as —C₆H₄OCH₃, —C₆H₄OCH₂CH₃,—C₆H₃(OCH₃)₂, or —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃, —C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, or—C₆H₄tBu.

R⁸ is preferably H, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C₆-C₂₄aryl,such as phenyl, naphthyl, or biphenyl.

Preferably, R⁹ and R¹⁰ are independently of each other H, C₁-C₁₈alkyl,such as n-butyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, such as—CH₂(OCH₂CH₂)_(w)OCH₃, w=1, 2, 3, or 4, C₆-C₂₄aryl, such as phenyl,naphthyl, or biphenyl, C₆-C₂₄aryl which is substituted by G, such as—C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃,—C₆H₃(CH₃)₂, —C₆H₂(CH₃), or —C₆H₄tBu, or R⁹ and R¹⁰ together form a 4 to8 membered ring, especially a 5 or 6 membered ring, such as cyclohexyl,or cyclopentyl.

Preferably, R^(14′) and R^(15′) are independently of each other H,C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, Iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, orbiphenyl.

D is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵is C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, orbiphenyl.

E is preferably —OR²⁹; —SR²⁹; —NR²⁵R²⁵; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁵; or—CN; wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each otherC₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₂₄aryl, suchas phenyl, naphthyl, or biphenyl. G is E, or C₁-C₁₈alkyl, such asmethyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl,hexyl, octyl, or 2-ethyl-hexyl.

Among the above-mentioned groups Ar² the following groups are preferred:

wherein R⁶, R⁷, R⁹ and R¹⁰ are defined as above and n1 and n2 are 1, 2,or 3.

The polymer of the present invention comprise the repeating unit of theformula I in an amount of from 0.5 mol % to 100 mol %, especially in anamount of from 20 mol % to 60 mol %, wherein the sum of all repeatingunits (monomers) is 100 mol %. Accordingly, the polymers of the presentinvention can comprise besides the repeating unit of the formula Iadditional repeating units in an amount of up to 99.5 mol %, especiallyin an amount of from 80 mol % to 40 mol %.

Suitable additional repeating units T are selected from the groupconsisting of

p is an integer from 1 to 10, especially 1, 2 or 3,q is an integer from 1 to 10, especially 1, 2 or 3,s is an integer from 1 to 10, especially 1, 2 or 3,R¹⁴ and R¹⁵ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G,R¹⁶ and R¹⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, or —CO—R²⁸,R¹⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—;R¹⁹ and R²⁰ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl,R¹⁹ and R²⁰ together form a group of formula ═CR¹⁰⁰R¹⁰¹, whereinR¹⁰⁰ and R¹⁰¹ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G, orR¹⁹ and R²⁰ form a ring, especially a five- or six-membered ring, andD and E are as defined above.

If R¹⁹ and R²⁰ together form a group of formula ═CR¹⁰⁰R¹⁰¹, T ispreferably a group of formula

wherein R¹⁰² and R¹⁰³ are independently of each other C₁-C₁₈alkyl,C₁-C₁₈alkoxy, C₆-C₁₀aryl, C₆-C₁₀aryloxy, or di(C₁-C₁₈alkyl)amino,wherein the aryl or aryloxy groups optionally can be substituted byC₁-C₈alkyl (cf. U.S. Pat. No. 6,512,083).

Preferred examples of T are selected from groups of formula

R¹⁶ and R¹⁷ are independently of each other H, C₁-C₁₈alkyl, such asmethyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl,t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, orn-heptyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,such as —CH₂OCH₃, —CH₂OCH₂CH₃, —CH₂OCH₂CH₂OCH₃, or —CH₂OCH₂CH₂OCH₂CH₃,C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl, C₆-C₂₄aryl which issubstituted by G, such as —C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, or—C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃, —C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, or —C₆H₄tBu,R¹⁸ is H, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl,isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C₆-C₂₄aryl, such asphenyl, naphthyl, or biphenyl, andR¹⁹ and R²⁰ are independently H, C₁-C₁₈alkyl, such as n-butyl,sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, such as —CH₂(OCH₂CH₂)_(w)OCH₃,w=1, 2, 3, or 4, C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl,C₆-C₂₄aryl which is substituted by G, such as —C₆H₄OCH₃, —C₆H₄OCH₂CH₃,—C₆H₃(OCH₃)₂, —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃, —C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, or—C₆H₄tBu, or R⁹ and R¹⁰ together form a 4 to 8 membered ring, especiallya 5 or 6 membered ring, such as cyclohexyl, or cyclopentyl.

Particularly preferred are co-monomers T, which are selected from thegroup consisting of

R¹⁶ and R¹⁷ are independently of each other C₁-C₁₈alkyl, especiallyC₄-C₁₂alkyl, which can be interrupted by one or two oxygen atoms,R¹⁸ is C₁-C₁₈alkyl, andR¹⁹ and R²⁰ are independently of each other C₁-C₁₈alkyl, especiallyC₄-C₁₂alkyl, which can be interrupted by one or two oxygen atoms, orR¹⁹ and R²⁰ form a five or six membered carbocyclic ring, whichoptionally can be substituted by C₁-C₄alkyl.

Especially preferred are polymers, comprising a repeating unit of theformula

and a co-monomer T in an amount of 0 to 99.5 mol %, especially in anamount of 40 to 80 mol %, wherein the sum of the repeating unit(s) andthe co-monomer is 100 mol %, whereinA¹ is hydrogen, or C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,A² is hydrogen, or C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,A³ is hydrogen, or C₁-C₁₈alkoxy, or C₁-C₁₈alkyl, such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl,2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,A⁴ is hydrogen, or C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,A⁵ is hydrogen, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,di(C₁-C₁₈alkyl)amino, or C₁-C₁₈alkoxy, such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy,2-methylbutoxy, n-pentoxy, isopentoxy, n-hexoxy, 2-ethylhexoxy, orn-heptoxy,A⁶ is hydrogen, or C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,A⁷ is hydrogen, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl, orC₁-C₁₈alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy,isobutoxy, sec-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, isopentoxy,n-hexoxy, 2-ethylhexoxy, or n-heptoxy, andT is a group of formula

wherein s is one or two,R¹⁶ and R¹⁷ are independently of each other C₁-C₁₈alkyl, especiallyC₄-C₁₂alkyl, especially hexyl, heptyl, 2-ethylhexyl, and octyl, whichcan be interrupted by one or two oxygen atoms, C₁-C₁₈alkoxy, especiallyC₄-C₁₂alkoxy, especially hexyloxy, heptyloxy, 2-ethylhexyloxy, andoctyloxy, which can be interrupted by one or two oxygen atoms,and R¹⁹ and R²⁰ are independently of each other C₁-C₁₈alkyl, especiallyC₄-C₁₂alkyl, especially hexyl, heptyl, 2-ethylhexyl, and octyl, whichcan be interrupted by one or two oxygen atoms.

In another aspect, the polymers of the present invention compriserepeating units of formula II. Examples of repeating units of theformula II are

wherein Ar⁴ is as defined above,R¹ and R² are independently of each other H, halogen, SO₃ ⁻,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or —CO—R²⁸,or two substituents R¹ and R², which are adjacent to each other, are agroup

D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; —OCOOR²⁷;or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; orR²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—,R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Repeating units of formula (IIe), (IIf), and (IIg) are most preferred.

Preferably, R¹ and R² are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, orsec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl.

D is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵is C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, orbiphenyl.

E is preferably —OR²⁹; —SR²⁹; —NR²⁵R²⁵; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁵; or—CN; wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each otherC₁-C₁₈ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₂₄ aryl,such as phenyl, naphthyl, or biphenyl. G is E, or C₁-C₁₈alkyl, such asmethyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl,hexyl, octyl, or 2-ethyl-hexyl.

Ar⁴ is preferably a group of formula

p is an integer from 1 to 10, especially 1, 2 or 3,q is an integer from 1 to 10, especially 1, 2 or 3,r is an integer of 0 to 10, in particular 0, 1, 2 or 3,R³ to R⁸ are independently of each other H, halogen, SO₃ ⁻, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅aralkyl, or —COR²⁸, ortwo substituents R³ to R⁸, which are adjacent to each other, are a group

R^(14′) and R^(15′) are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G,R¹⁶ is C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, which optionally can be substituted,whereinD is —CO—; —COO—; —S—; —SO—; —SO₂—, —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; —OCOOR²⁷;or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; orR²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Preferably, R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are independently of each other H,C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl,n-hexyl, 2-ethylhexyl, or n-heptyl, C₁-C₁₈alkyl which is substituted byE and/or interrupted by D, such as —CH₂OCH₃, —CH₂OCH₂CH₃,—CH₂OCH₂CH₂OCH₃, or —CH₂OCH₂CH₂OCH₂CH₃, C₆-C₂₄aryl, such as phenyl,naphthyl, or biphenyl, C₆-C₂₄aryl which is substituted by G, such as—C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, or —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃,—C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, or —C₆H₄tBu.

Preferably, R^(14′) and R^(15′) are independently of each other H,C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, and sec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, andbiphenyl.

R¹⁶ is preferably H, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, and sec-butyl, or C₆-C₂₄aryl, such asphenyl, naphthyl, and biphenyl.

D is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR²⁵—, wherein R²⁵is C₁-C₁₈ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, t-butyl, hexyl, octyl, and 2-ethyl-hexyl, orC₆-C₂₄aryl, such as phenyl, naphthyl, and biphenyl.

E is preferably —OR²⁹, —SR²⁹, —NR²⁵R²⁵, —COR²⁸, —COOR²⁷, —CONR²⁵R²⁵, or—CN, wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each otherC₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, 2-ethyl-hexyl, or C₆-C₂₄aryl, such asphenyl, naphthyl, and biphenyl. G is E, or C₁-C₁₈alkyl, such as methyl,ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl,2-ethyl-hexyl.

Another aspect of the present invention, is directed to polymers,comprising repeating units of the formula

whereinAr⁵ and Ar⁶ are independently of each other an aryl group, or aheteroaryl group, which can optionally be substituted, especially aC₆-C₃₀aryl group, or a C₂-C₂₈heteroaryl group, which can optionally besubstituted.

The repeating unit of formula III is not a repeating unit of formula

especially Ar⁶ is not a phenyl group substituted by a hydroxy group inortho position to the bonding to the benzotriazole unit

Examples of

are groups of the following formula

wherein A²¹, A²², A²³, A²⁴, A¹¹, A¹², A¹³, A¹⁴′, A¹⁵, A¹⁶, A¹⁷ and A¹⁸are independently of each other H, halogen, SO₃ ⁻, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₈-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or —CO—R²⁸,wherein E, D, G and R²⁸ are defined as above, or two groups A¹¹, A¹²,A¹³, A¹⁴′, A¹⁵, A¹⁶, A¹⁷ and A¹⁸, which are neighbouring to each other,are a group

wherein A³¹, A³², A³³, A³⁴, A³⁵, A³⁶ and A³⁷ are independently of eachother H, halogen, SO₃ ⁻, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby E and/or interrupted by D, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —CO—R²⁸.

Examples of Ar⁶ are groups of formula

wherein the dotted line represent the bond to the benzotriazole ring;R⁵⁶ and R⁵⁷ are independently of each other H; C₁-C₁₈alkyl; C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D; C₆-C₂₄aryl;C₆-C₂₄aryl which is substituted by G; C₂-C₂₀heteroaryl; C₂-C₂₀heteroarylwhich is substituted by G; C₂-C₁₈alkenyl; C₂-C₁₈alkynyl; C₁-C₁₈alkoxy;C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D; orC₇-C₂₅aralkyl;R⁵⁸ is H; C₁-C₁₈alkyl; C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D; C₆-C₂₄aryl; or C₇-C₂₅aralkyl;R⁵⁹ and R⁶⁰ are independently of each other H; C₁-C₁₈alkyl; C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D; C₆-C₂₄aryl;C₆-C₂₄aryl which is substituted by G; C₂-C₂₀heteroaryl; C₂-C₂₀heteroarylwhich is substituted by G; C₂-C₁₈alkenyl; C₂-C₁₈alkynyl; C₁-C₁₈alkoxy;C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D; orC₇-C₂₅aralkyl;R⁷¹ is H, C₁-C₁₈alkyl, —C≡N, —CONR²⁵R²⁶ or —COOR²⁷,D is —CO—; —COO—; —OCOO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—;—POR³²—; —CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; —OCOOR²⁷;or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³; R²⁴; R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl; C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; orR²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—, andR²⁹is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Most preferred, Ar⁶ is a group of the formula

wherein the dotted line represent the bond to the benzotriazole ring andR⁷¹ is H, alkyl, —C≡N, or —COOR²⁷, wherein R²⁷ is H, or C₁-C₁₈alkyl,which optionally can be interrupted by one or more oxygen atoms,especially C₄-C₁₂alkyl, which can be interrupted by one or two oxygenatoms.

The polymer of the present invention comprise the repeating unit of theformula II and/or III in an amount of from 0.5 mol % to 100 mol %,especially in an amount of from 20 mol % to 80 mol %, wherein the sum ofall repeating units (monomers) is 100 mol %. Accordingly, the polymersof the present invention can comprise besides the repeating unit of theformula II and/or III additional repeating units in an amount of up to99.5 mol %, especially in an amount of from 80 mol % to 40 mol %.Suitable additional repeating units are the repeating units T describedfor the polymers comprising repeating units of the formula I.

As stated above among the repeating units of the formula IV, repeatingunits of the formula

against repeating units of the formula

whereinAr⁷, Ar^(7′), Ar⁸ and Ar^(8′) are independently of each other aC₆-C₃₀aryl group, or a C₂-C₂₆heteroaryl group, which can optionally besubstituted,X¹ and X² are independently of each other a group of the formula

wherein the dotted line represent the bond to the benzotriazole unit,R⁵⁶ and R⁵⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl,R⁵⁸ is H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, or C₇-C₂₅aralkyl,R⁵⁹ and R⁶⁰ are independently of each other H, C₁-C₁₈ alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroarylwhich is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl, or R⁵⁹ and R⁶⁰ form a ring, especially a five- orsix-membered ring,R⁷¹ is H, C₁-C₁₈alkyl, —C≡N, —CONR²⁵R²⁶ or —COOR²⁷,D is —CO—; —COO—; —OCOO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—;—POR³²—; —CR²³═CR²⁴—; or —C≡C—; andE is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷; —CONR²⁵R²⁶; —CN; —OCOOR²⁷;or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³, R²⁴, R²⁵ and R²⁶are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; orR²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—, andR²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R³⁰ and R³¹ independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andR³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Preferably, R⁵⁶ and R⁵⁷ are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl,2-ethylhexyl, and n-heptyl, C₁-C₁₈alkyl, which is substituted by Eand/or interrupted by D, such as —CH₂OCH₃, —CH₂OCH₂CH₃, —CH₂OCH₂CH₂OCH₃,and —CH₂OCH₂CH₂OCH₂CH₃, C₆-C₂₄aryl, such as phenyl, naphthyl, andbiphenyl, or C₆-C₂₄aryl, which is substituted by g, such as —C₆H₄OCH₃,—C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃, —C₆H₃(CH₃)₂,—C₆H₂(CH₃)₃, and —C₆H₄tBu.

R⁵⁸ is preferably H, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, and n-heptyl, or C₆-C₂₄aryl,such as phenyl, naphthyl, and biphenyl.

Preferably, R⁵⁹ and R⁶⁰ are independently of each other H, C₁-C₁₈alkyl,such as n-butyl, sec-butyl, hexyl, octyl, and 2-ethyl-hexyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, such as—CH₂(OCH₂CH₂)_(w)OCH₃, w=1, 2, 3, or 4, C₆-C₂₄aryl, such as phenyl,naphthyl, and biphenyl, C₆-C₂₄aryl which is substituted by G, such as—C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, —C₆H₃(OCH₂CH₃)₂, —C₆H₄CH₃,—C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, and —C₆H₄tBu, or R⁵⁹ and R⁶⁰ together form a 4to 8 membered ring, preferably a 5 or 6 membered ring, such ascyclohexyl, and cyclopentyl.

R⁷¹ is preferably H, —CONR²⁵R²⁵ or —CN, wherein R²⁵ is H, C₁-C₁₈alkyl,or C₆-C₂₄aryl, such as phenyl, naphthyl, and biphenyl.

Most preferred are polymers, comprising a repeating unit of the formula

and/or

and a repeating unit T in an amount of 0 to 99.5 mol %, especially in anamount of 40 to 80 mol %, wherein the sum of the repeating unit(s) andthe co-monomer is 100 mol %, wherein

wherein the dotted line is the bond to the nitrogen atom of thebenzotriazole unit,

wherein the dotted lines are the bonds to the nitrogen atoms of thebenzotriazole unit, A⁴¹ is hydrogen, C₁-C₁₈alkoxy, or C₁-C₁₈alkyl, suchas methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl,t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, orn-heptyl,A⁴² is hydrogen, or C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,A⁴³ is hydrogen, or C₁-C₁₈alkoxy, or C₁-C₁₈alkyl, such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl,2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl,X¹ and X² are independently of each other a group of the formula

wherein the dotted line represent the bond to the benzotriazole unit,R⁷¹ is H, C₁-C₁₈alkyl, —C≡N, or —COOR²⁷, whereinR²⁷ is H; or C₁-C₁₈alkyl, which can be interrupted by one or more oxygenatoms, especially C₄-C₁₂alkyl, which can be interrupted by one or twooxygen atoms, andT is a group of formula

wherein R⁵⁹ and R⁶⁰ independently of each other C₁-C₁₈alkyl, especiallyC₄-C₁₂alkyl, which can be interrupted by one or two oxygen atoms.

The polymers of this invention preferably have a weight averagemolecular weight of 50,000 Daltons or greater, more preferably 100,000Daltons or greater, and most preferably 150,000 Daltons or greater;preferably 1,000,000 Daltons or less, more preferably 500,000 Daltons orless and most preferably 250,000 Daltons or less. Molecular weights aredetermined according to gel permeation chromatography using polystyrenestandards.

A further embodiment of the present invention is represented by themonomers of the formula

x and y are 0 or 1,Ar¹, Ar², Ar³, Ar⁴, Ar⁵ and Ar⁶ are Independently of each other an arylgroup, or a heteroaryl group, which optionally can be substituted,especially a C₆-C₃₀aryl group, or a C₂-C₂₆heteroaryl group, which canoptionally be substituted, andX¹¹ is independently in each occurrence a halogen atom, or —B(OH)₂,—B(OY¹)₂ or

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,which are starting materials in the preparation of the polymers offormula I to IV.

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₁₈alkyl is a branched or unbranched radical such as for examplemethyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl.

C₁-C₁₈perfluoroalkyl is a branched or unbranched radical such as forexample —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

C₁-C₁₈alkoxy radicals are straight-chain or branched alkoxy radicals,e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.

C₂-C₁₈alkenyl radicals are straight-chain or branched alkenyl radicals,such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl,isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec enyl.

C₂-C₂₄alkynyl is straight-chain or branched and preferably C₂₋₈alkynyl,which may be unsubstituted or substituted, such as, for example,ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

C₄-C₁₈cycloalkyl is preferably C₅-C₁₂cycloalkyl, such as, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cyclododecyl. Cyclohexyl and cyclopentyl are most preferred.

C₂-C₁₈alkenyl is for example vinyl, allyl, butenyl, pentenyl, hexenyl,heptenyl, or octenyl.

Aryl is usually C₆-C₃₀aryl, preferably C₆-C₂₄aryl, which optionally canbe substituted, such as, for example, phenyl, 4-methylphenyl,4-methoxyphenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl,anthryl, tetracyl, pentacyl, hexacyl, terphenylyl or quadphenylyl.

C₇-C₂₄aralkyl radicals are preferably C₇-C₁₅aralkyl radicals, which maybe substituted, such as, for example, benzyl, 2-benzyl-2-propyl,β-phenethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl,ω-phenyl-dodecyl or 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl.

C₂-C₂₆heteroaryl is a ring with five to seven ring atoms or a condensedrig system, wherein nitrogen, oxygen or sulfur are the possible heteroatoms, and is typically an unsaturated heterocyclic radical with five to30 atoms having at least six conjugated π-electrons such as thienyl,benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl,2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl,phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl,triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl,indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl,phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl,pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl,phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl,isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl,which can be unsubstituted or substituted.

Examples of a five or six membered ring formed by R⁶ and R⁷ and R⁵⁶ andR⁵⁷, respectively are heterocycloalkanes or heterocycloalkenes havingfrom 3 to 5 carbon atoms which can have one additional hetero atomselected from nitrogen, oxygen and sulfur, for example

which can be part of a bicyclic system, for example

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, acarboxyl group, an ester group, a carbamoyl group, an amino group, anitro group or a silyl group.

The term “haloalkyl” means groups given by partially or whollysubstituting the above-mentioned alkyl group with halogen, such astrifluoromethyl etc. The “aldehyde group, ketone group, ester group,carbamoyl group and amino group” include those substituted by anC₁-C₁₈alkyl group, a C₄-C₁₈cycloalkyl group, an C₆-C₃₀aryl group, anC₇-C₂₄aralkyl group or a heterocylic group, wherein the alkyl group, thecycloalkyl group, the aryl group, the aralkyl group and the heterocyclicgroup may be unsubstituted or substituted. The term “silyl group” meansa group of formula —SiR¹⁰⁵R¹⁰⁶R¹⁰⁷, wherein R¹⁰⁵, R¹⁰⁶ and R¹⁰⁷ areindependently of each other a C₁-C₈alkyl group, in particular aC₁-C₄alkyl group, a C₈-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as atrimethylsilyl group.

If a substituent, such as, for example R⁶, R⁷, R⁵⁶ and R⁵⁷, occurs morethan one time in a group, it can be different in each occurrence.

As described above, the aforementioned radicals may be substituted by Eand/or, if desired, interrupted by D. Interruptions are of coursepossible only in the case of radicals containing at least 2 carbon atomsconnected to one another by single bonds; C₆-C₁₈aryl is not interrupted;interrupted arylalkyl or alkylaryl contains the unit D in the alkylmoiety. C₁-C₁₈alkyl substituted by one or more E and/or interrupted byone or more units D is, for example, (CH₂CH₂O)_(n)—R^(x), where n is anumber from the range 1-9 and R^(x) is H or C₁-C₁₀alkyl orC₂-C₁₀alkanoyl (e.g. CO—CH(C₂H₅)C₄H₉), CH₂—CH(OR^(y′))—CH₂—O—R^(y),where R^(y) is C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₁₅phenylalkyl,and R^(y′) embraces the same definitions as R^(y) or is H;C₁-C₈alkylene-COO—R^(z), e.g. CH₂COOR^(z), CH(CH₃)COOR^(z),C(CH₃)COOR^(z), where R^(z) is H, C₁-C₁₈alkyl, (CH₂CH₂O)₁₋₉—R^(x), andR^(x) embraces the definitions indicated above; CH₂CH₂—O—CO—CH═CH₂;CH₂CH(OH)CH₂—O—CO—C(CH₃)═CH₂.

The polymers containing groups of formulas (I), (II), (III) and (IV) maybe prepared by any suitable process, but are preferably prepared by theprocesses described below. The condensation reaction of an aromaticboronate and a bromide, commonly referred to as the “Suzuki reaction”,is tolerant of the presence of a variety of organic functional groupsand as reported by N. Miyaua and A Suzuki in Chemical Reviews, Vol. 95,pp. 457-2483 (1995). This reaction can be applied to preparing highmolecular weight polymers and copolymers.

To prepare polymers corresponding to formula (I), (II), (III) or (IV), adibromide corresponding to formula V, VI, VII, or VIII, or a mixturethereof is reacted with an equimolar amount of diboronic acid ordiboronate corresponding to formula V, VI, VII, or VIII, or a mixturethereof, preferably a co-monomer

wherein X¹¹ is independently in each occurrence a halogen atom, or—B(OH)₂, —B(OY¹)₂ or

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—,under the catalytic action of Pd and triphenylphosphine. The reaction istypically conducted at about 70° C. to 120° C. in an aromatichydrocarbon solvent such as toluene. Other solvents such asdimethylformamide and tetrahydrofuran can also be used alone, or inmixtures with an aromatic hydrocarbon. An aqueous base, preferablysodium carbonate or bicarbonate, is used as the HBr scavenger. Dependingon the reactivities of the reactants, a polymerization reaction may take2 to 100 hours. Organic bases, such as, for example, tetraalkylammoniumhydroxide, and phase transfer catalysts, such as, for example TBAB, canpromote the activity of the boron (see, for example, Leadbeater & Marco;Angew. Chem. Int. Ed., 2003, 42, 1407 and references cited therein).Other variations of reaction conditions are given by T. I. Wallow and B.M. Novak in Journal of Organic Chemistry, Vol. 59, pp. 5034-5037 (1994);and M. Remmers, M. Schulze, and G. Wegner in Macromolecular RapidCommunications, Vol. 17, pp. 239-252 (1996).

An alternating copolymer results when a dibromide corresponding toformula V, VI, VII, or VIII is reacted with a diboronate correspondingto formula

wherein X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂ or

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, or —C(CH₃)₂CH₂C(CH₃)₂—.If desired, a monofunctional aryl halide or aryl boronate may be used asa chain-terminator in such reactions, which will result in the formationof a terminal aryl group.

Polymerization processes involving only dihalo-functional reactants maybe carried out using nickel coupling reactions. One such couplingreaction was described by Colon et al. in Journal of Polymer Science,Part A, Polymer Chemistry Edition, Vol. 28, p. 367 (1990), and by Colonet al. in Journal of Organic Chemistry, Vol. 51, p. 2627 (1986). Thereaction is typically conducted in a polar aprotic solvent (e.g.,dimethylacetamide) with a catalytic amount of nickel salt, a substantialamount of triphenylphosphine and a large excess of zinc dust. A variantof this process is described by Ioyda et al. in Bulletin of the ChemicalSociety of Japan, Vol. 63, p. 80 (1990) wherein an organo-soluble iodidewas used as an accelerator. Another nickel-coupling reaction wasdisclosed by Yamamoto in Progress in Polymer Science, Vol. 17, p. 1153(1992) wherein a mixture of dihaloaromatic compounds were treated withan excess amount of nickel (1,5-cyclooctadiene) complex in an inertsolvent. All nickel-coupling reactions when applied to reactant mixturesof two or more aromatic dihalides yield essentially random copolymers.Such polymerization reactions may be terminated by the addition of smallamounts of water to the polymerization reaction mixture, which willreplace the terminal halogen groups with hydrogen groups. Alternatively,a monofunctional aryl halide may be used as a chain-terminator in suchreactions, which will result in the formation of a terminal aryl group.

In one embodiment, the polymers of the invention contain conjugatedgroups other than the benzotriazole groups described above. “Conjugatedgroups” refer to moieties containing double bonds, triple bonds and/oraromatic rings. Examples of such groups are the above mentionedco-monomers T. The incorporation of such groups into the polymer may beused to modify the light absorption, ionization potential, and/orelectronic properties of the polymer. Such polymers may be preparedusing the methods described above incorporating at least one conjugatedcompound different from the benzotriazole compounds described above.Such conjugated compounds, hereinafter referred to as “comonomers”, havefunctional groups which permit them to copolymerize with thebenzotriazole compounds. For example, dihalo-functional comonomers arepreferably used in conjunction with dihalo-functional benzotriazolecompounds in nickel-coupling polymerization reactions; dihalo-functionalcomonomers are preferably used in conjunction withbenzotriazole-diboronic acids or benzotriazole-diboronates; andconjugated comonomers bearing diboronic acid or diboronatefunctionalities are preferably used in conjunction withdihalobenzotriazoles. For the purpose of preparing polymers of theinvention, more than one diboronic acid/diboronate and more than onedibromide may be used in a Suzuki polymerization reaction so long as thetotal molar amount of diboronic acids/diboronates is essentiallyequivalent to the total amount of dibromides.

Nickel-coupling polymerizations yield essentially random copolymerscomprising benzotriazole group-containing units and units derived fromother co-monomers, while Suzuki polymerizations yield alternatingcopolymers.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction. For instance, a high molecular weightcopolymer comprising mainly large blocks of benzotriazole homopolymersconnected to short blocks of alternating benzotriazole co-monomeroligomers may be made by first introducing into the reaction reactantsin the appropriate ratio to make the alternating benzotriazole-comonomeroligomers followed by the remainder of benzotriazole monomers so long asthere is an overall balance of boronic and bromo groups.

Usually the polymers of the present invention comprise end moieties E¹,wherein E¹ is hydrogen or an aryl moiety which may optionally besubstituted with a reactive group capable of undergoing chain extensionor crosslinking, or a tri(C₁-C₁₈)alkylsiloxy group. As used herein, areactive group capable of undergoing chain extension or crosslinkingrefers to any group which is capable of reacting with another of thesame group or another group so as to form a link to prepare oligomers orpolymers. Preferably, such reactive group is a hydroxy, glycidyl ether,acrylate ester, methacrylate ester, ethenyl, ethynyl, maleimide,nadimide, trifluorovinyl ether moiety or a cyclobutene moiety fused tothe aromatic ring of E¹.

The polymers of the present invention, where E¹ are reactive groups asdefined above, are capable of crosslinking to form solvent resistant,heat-resistant films at 100° C. or more, more preferably at 150° C. ormore. Preferably, such crosslinking occurs at 350° C. or less, morepreferably 300° C. or less and most preferably 250° C. or less. Thecrosslinkable polymers of the invention are stable at 100° C. or moreand more preferably 150° C. or more. “Stable” as used herein means thatsuch polymers do not undergo crosslinking or polymerization reactions ator below the stated temperatures. If a crosslinkable material isdesired, E¹ is preferably a vinylphenyl, an ethynylphenyl, or 4-(or3-)benzocyclobutenyl radical. In another embodiment, E¹ is selected froma group of phenolic derivatives of the formula —C₆H₄—O—Y, wherein Y is

If desired, the crosslinkable groups can be present in other parts ofthe polymer chain. For example, one of the substituents of theco-monomer T may be a crosslinkable group E¹.

The end-capping agent E¹-X (E¹ is as defined above and X is either Cl orBr) is incorporated into the polymers of the present invention under thecondition in which the resulting polymers are substantially capped bythe reactive group E¹. The reactions useful for this purpose are thenickel-coupling and Suzuki reactions described above. The average degreeof polymerization is controlled by the mole ratio of monomers toend-capping agent.

Depending on the process of preparation the polymers of the presentinvention can be block copolymers, random copolymers, or alternatingcopolymers.

Another aspect of this invention is related to polymer blends containing1 to 99 percent of at least one benzotriazole containing polymers ofthis invention. The remainder 1 percent to 99 percent of the blend iscomposed of one or more polymeric materials selected from among chaingrowth polymers such as polystyrene, polybutadiene, poly(methylmethacrylate), and poly(ethylene oxide); step-growth polymers such asphenoxy resins, polycarbonates, polyamides, polyesters, polyurethanes,and polyimides; and crosslinked polymers such as crosslinked epoxyresins, crosslinked phenolic resins, crosslinked acrylate resins, andcrosslinked urethane resins. Examples of these polymers may be found inPreparative Methods of Polymer Chemistry, W. R. Sorenson and T. W.Campbell, Second Edition, Interscience Publishers (1968). Also may beused in the blends are conjugated polymers such as poly(phenylenevinylene), substituted poly(phenylene vinylene)s, substitutedpolyphenylenes and polythiophenes. Examples of these conjugated polymersare given by Greenham and Friend in Solid State Physics, Vol. 49, pp.1-149 (1995).

Another aspect of the invention is the films formed from the polymers ofthe invention. Such films can be used in polymeric light-emittingdiodes. Preferably, such films are used as emitting layers. Thesepolymers may also be used as protective coatings for electronic devicesand as fluorescent coatings. The thickness of the coating or film isdependent upon the ultimate use. Generally, such thickness can be from0.01 to 200 microns. In that embodiment wherein the coating is used as afluorescent coating, the coating or film thickness is from 50 to 200microns. In that embodiment where the coatings are used as electronicprotective layers, the thickness of the coating can be from 5 to 20microns. In that embodiment where the coatings are used in a polymericlight-emitting diode, the thickness of the layer formed is 0.01 to 2microns. The polymers of the invention form good pinhole- anddefect-free films. Such films can be prepared by means well known in theart including spin-coating, spray-coating, dip-coating androller-coating. Such coatings are prepared by a process comprisingapplying a composition to a substrate and exposing the appliedcomposition to conditions such that a film is formed. The conditionswhich form a film depend upon the application technique. In a preferredembodiment, the composition applied to the substrate comprises thebenzotriazole polymers dissolved in a common organic solvent.Preferably, the solution contains from 0.1 to 10 weight percent of thepolymers. This composition is applied to the appropriate substrate bythe desired method and the solvent is allowed to evaporate. Residualsolvent may be removed by vacuum and/or by heat. After removal of thesolvent, the coating is then exposed to the necessary conditions to curethe film, if needed, to prepare a film having high solvent and heatresistance. The films are preferably substantially uniform in thicknessand substantially free of pinholes. In another embodiment, the polymersmay be partially cured. This is known as B-staging.

A further embodiment of the present invention is directed to an opticaldevice or a component therefore, comprising a substrate and a polymeraccording to the present invention.

A device according to the present invention may be prepared Inaccordance with the disclosure of WO99/48160, the contents of which areincorporated by reference. Polymers according to the present inventionmay be present in the device as the sole light emitting polymer or as acomponent in a blend further comprising hole and/or electrontransporting polymers. Alternatively, the device may comprise distinctlayers of a polymer of the present invention, a hole transportingpolymer and/or an electron transporting polymer.

In one embodiment the optical device comprises an electroluminescentdevice, which comprises at least

(a) a reflective or transmissive anode

(b) a reflective or transmissive cathode

(c) an emissive layer comprising a polymer according to the presentinvention located between the electrodes

and optionally

(d) a charge injecting layer for injecting positive charge carriers, and

(e) a charge injecting layer for injecting negative charge carriers.

The layer (d) may be a positive charge carrier transport layer which islocated between the light emissive layer (c) and an anode electrodelayer, or may be an anode electrode layer. The layer (e) may be anegative charge carrier transport layer which is located between thelight emissive layer (c) and a cathode electrode layer, or may be ancathode electrode layer. Optionally, an organic charge transport layercan be located between the light emissive layer (c) and one of thecharge carrier injecting layers (d) and (e).

The EL device emits light below 520 nm, especially between 380 nm and520 nm, very especially between 400 nm and 490 nm. The EL device emitsblue light.

The EL device has a NTSC coordinate of between about (0.10, 0.02) andabout (0.25, 0.25), especially a NTSC coordinate of about (0.14, 0.08).

It will be appreciated that the light emissive layer may be formed froma blend or mixture of materials including one or more polymers accordingto the present invention, and optionally further different polymers. Thefurther different polymers may be so-called hole transport polymers(i.e. to improve the efficiency of hole transport to the light-emissivematerial) or electron-transport polymers (i.e. to improve the efficiencyof electron transport to the light-emissive material). Preferably, theblend or mixture would comprise at least 0.1% by weight of a polymeraccording to the present invention, preferably from 0.2 to 50%, morepreferably from 0.5 to 30% by weight.

The light-emitting layer can be comprised of a single material, but morecommonly consists of a host material, i.e. the polymers of the presentinvention, doped with a guest compound or compounds, where lightemission comes primarily from the dopant and can be of any color. Thedopant is usually chosen from highly fluorescent dyes, butphosphorescent compounds, e.g., transition metal complexes as describedin WO 98/55561, WO 00/18851, WO 00/57676, and WO 00/70655 are alsouseful. The polymers of the present invention may also be employed asdopants within other host materials. Dopants are typically coated as0.01 to 10% by weigh into the host material.

Host and emitting molecules known to be of use include, but are notlimited to, those disclosed in U.S. Pat. Nos. 4,768,29; 5,141,671;5,150,006; 5,151,629; 5,294,870; 5,405,709; 5,484,922; 5,593,788;5,645,948; 5,683,823; 5,755,999; 5,928,802; 5,935,720; 5,935,721; and6,020,078.

An organic EL device typically consists of an organic film sandwichedbetween an anode and a cathode such that when a forward bias is appliedto the device, holes are injected into the organic film from the anode,and electrons are injected into the organic film from the cathode. Thecombination of a hole and an electron may give rise to an exciton, whichmay undergo radiative decay to the ground state by liberating a photon.In practice the anode is commonly a mixed oxide of tin and indium forits conductivity and transparency. The mixed oxide (ITO) is deposited ona transparent substrate such as glass or plastic so that the lightemitted by the organic film may be observed. The organic film may be thecomposite of several individual layers each designed for a distinctfunction. Since holes are injected from the anode, the layer next to theanode needs to have the functionality of transporting holes. Similarly,the layer next to the cathode needs to have the functionality oftransporting electrons. In many instances, the electron-(hole)transporting layer also acts as the emitting layer. In some instancesone layer can perform the combined functions of hole and electrontransport and light emission. The individual layers of the organic filmmay be all polymeric in nature or combinations of films of polymers andfilms of small molecules deposited by thermal evaporation. It ispreferred that the total thickness of the organic film be less than 1000nanometers (nm). It is more preferred that the total thickness be lessthan 500 nm. It is most preferred that the total thickness be less than300 nm. It is preferred that the thickness of the active (lightemitting) layer be less than 400 nanometers (nm). It is more preferredthat the thickness is in the range of from 40 to 160 nm.

The ITO-glass which serves as the substrate and the anode may be usedfor coating after the usual cleaning with detergent, organic solventsand UV-ozone treatment. It may also be first coated with a thin layer ofa conducting substance to facilitate hole injection. Such substancesinclude copper phthalocyanine, polyaniline andpoly(3,4-ethylenedioxy-thiophene) (PEDOT); the last two in theirconductive forms by doping with a strong organic acid, e.g.,poly(styrenesulfonic acid). It is preferred that the thickness of thislayer be 200 nm or less; it is more preferred that the thickness be 100nm or less.

In the cases where a hole-transporting layer is used, the polymericarylamines described in U.S. Pat. No. 5,728,801, may be used. Otherknown hole-conducting polymers, such as polyvinylcarbazole, may also beused. The resistance of this layer to erosion by the solution of thepolymer film which is to be applied next is obviously critical to thesuccessful fabrication of multi-layer devices. The thickness of thislayer may be 500 nm or less, preferably 300 nm or less, most preferably150 nm or less.

In the case where an electron-transporting layer is used, it may beapplied either by thermal evaporation of low molecular weight materialsor by solution coating of a polymer with a solvent that would not causesignificant damage to the underlying film.

Examples of low molecular weight materials include the metal complexesof 8-hydroxyquinoline (as described by Burrows et al. in Applied PhysicsLetters, Vol. 64, pp. 2718-2720 (1994)), metallic complexes of10-hydroxybenzo(h)quinoline (as described by Hamada et al. in ChemistryLetters, pp. 906-906 (1993)), 1,3,4-oxadiazoles (as described by Hamadaet al. in Optoelectronics-Devices and Technologies, Vol. 7, pp. 83-93(1992)), 1,3,4-triazoles (as described by Kido et al. in ChemistryLetters, pp. 47-48 (1996)), and dicarboximides of perylene (as describedby Yoshida et al. in Applied Physics Letters, Vol. 69, pp. 734-736(1996)). Further examples of low molecular weight materials aredisclosed in the European patent application no. 03100972.3, the contentof which is incorporated herein by reference.

Polymeric electron-transporting materials are exemplified by1,3,4-oxadiazole-containing polymers (as described by Li et al. inJournal of Chemical Society, pp. 2211-2212 (1995), by Yang and Pei inJournal of Applied Physics, Vol 77, pp. 4807-4809 (1995)),1,3,4-triazole-containing polymers (as described by Strukelj et al. inScience, Vol. 267, pp. 1969-1972 (1995)), quinoxaline-containingpolymers (as described by Yamamoto et al. in Japan Journal of AppliedPhysics, Vol. 33, pp. L250-L253 (1994), O'Brien et al. in SyntheticMetals, Vol. 76, pp. 105-108 (1996)), and cyano-PPV (as described byWeaver et al. in Thin Solid Films, Vol. 273, pp. 39-47 (1996)). Thethickness of this layer may be 500 nm or less, preferably 300 nm orless, most preferably 150 nm or less.

The cathode may be deposited either by thermal evaporation or bysputtering and may consist of a number of layers. The thickness of thecathode material may be from 100 nm to 10,000 nm. The preferred metalsare calcium, barium, magnesium, indium, lithium fluoride (LiF),Caesiumfluoride (Csf), Ca(acac) and aluminum. Mixtures or alloys ofthese materials may also be used.

In a preferred embodiment, the electroluminescent device comprises atleast one hole-transporting polymer film and a light-emitting polymerfilm comprised of the polymer of the invention, arranged between ananode material and a cathode material such that under an appliedvoltage, holes are injected from the anode material into thehole-transporting polymer film and electrons are injected from thecathode material into the light-emitting polymer films when the deviceis forward biased, resulting in light emission from the light-emittinglayer.

In another preferred embodiment, layers of hole-transporting polymersare arranged so that the layer closest to the anode has the loweroxidation potential, with the adjacent layers having progressivelyhigher oxidation potentials. By these methods, electroluminescentdevices having relatively high light output per unit voltage may beprepared.

The term “hole-transporting polymer film” as used herein refers to alayer of a film of a polymer which when disposed between two electrodesto which a field is applied and holes are injected from the anode,permits adequate transport of holes into the emitting polymer.Hole-transporting polymers are typicallypoly(3,4-ethylenedioxy-thiophene) (PEDOT),PEDOT-PSS(PSS=poly(styrenesulfonic acid), polyaniline (PANI) andpolythiophenes. The term “light-emitting polymer film” as used hereinrefers to a layer of a film of a polymer whose excited states can relaxto the ground state by emitting photons, preferably corresponding towavelengths in the visible range. The term “anode material” as usedherein refers to a semi transparent, or transparent, conducting filmwith a work function between 4.5 electron volts (eV) and 5.5 eV.Examples are gold, silver, copper, aluminum, indium, iron, zinc, fin,chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungstenand the like, metallic alloys such as magnesium/copper,magnesium/silver, magnesium/aluminum, aluminum/indium and the like,semiconductors such as Si, Ge, GaAs and the like, metallic oxides suchas indium-tin-oxide (“ITO”), ZnO and the like, metallic compounds, andfurthermore, electroconducting polymers such polyacetylene, polypyrrole,polyparaphenylene and the like. Oxides and mixed oxides of indium andtin, and gold are preferred. Most preferred is ITO, especially ITO onglass or plastic as substrate. The term “cathode material” as usedherein refers to a conducting film with a work function between 2.5 eVand 4.5 eV. Examples are alkali metals, alkaline earth metals, group 13elements, silver, and copper as well as alloys or mixtures thereof suchas sodium, lithium, potassium, calcium, barium, lithium fluoride (LiF),caesium fluoride (CsF), sodium-potassium alloy, magnesium,magnesium-silver alloy, magnesium-copper alloy, magnesium-aluminumalloy, magnesium-indium alloy, aluminum, aluminum-aluminum oxide alloy,aluminum-lithium alloy, Indium, calcium, and materials exemplified inEP-A 499,011, such as electroconducting polymers e.g. polypyrrole,polythiophene, polyaniline, polyacetylene etc. Preferably lithium,calcium, barium, CsF, LiF, magnesium, indium, silver, aluminum, orblends and alloys of the above are used. In the case of using a metal ora metallic alloy as a material for an electrode, the electrode can beformed also by the vacuum deposition method. In the case of using ametal or a metallic alloy as a material forming an electrode, theelectrode can be formed, furthermore, by the chemical plating method(see for example, Handbook of Electrochemistry, pp 383-387, Mazuren,1985).

As methods for forming said thin films, there are, for example, thevacuum deposition method, the spin-coating method, the casting method,the Langmuir-Blodgett (“LB”) method, the ink jet printing method and thelike. Among these methods, the vacuum deposition method, the spin-matingmethod, the ink jet printing method and the casting method areparticularly preferred In view of ease of operation and cost.

In the case of forming the layers by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution prepared by dissolving the composition in aconcentration of from 0.0001 to 90% by weight in an appropriate organicsolvent such as benzene, toluene, xylene, chlorobenzene,tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,chloroform, dichloromethane, dimethylsulfoxide and the like. Thepolymers should be completely soluble in the employed solvents.

The organic EL device of the present invention has significantindustrial values since it can be adapted for a flat panel display of anon-wall television set, a flat light-emitting device, a light source fora copying machine or a printer, a light source for a liquid crystaldisplay or counter, a display signboard and a signal light. The polymersand compositions of the present invention can be used in the fields ofan organic EL device, a photovoltaic device, an electrophotographicphotoreceptor, a photoelectric converter, a solar cell, an image sensor,and the like.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight.

EXAMPLES Example 1

Bis(1,5-cyclooctadiene)nickel(0) (2.0 g, 7.27 mmol) and 2,2′-bipyridyl(1.14 g, 7.27 mmol) are dissolved in anhydrous toluene (7.0 ml) andstirred at 80° C. for 1 hour under an argon atmosphere in the dark.Monomer 1 (0.23 g, 0.60 mmol) and 2,7-dibromo-9,9-dihexylfluorene(Monomer 2) (1.50 g, 3.05 mmol) are dissolved in anhydrous toluene (7.0ml) and purged thoroughly with argon, then added to the solution of Nicomplex and stirred at 80° C. for 17 hours under argon in the dark.Anhydrous toluene (7.0 ml) is added and the reaction allowed to progressa further 5 hours. Bromobenzene (1 ml, 9.5 mmol) is added and thereaction stirred for a further 2 hours. The reaction mixture is pouredinto stirred methanol/c.HCl_((aq)) (10:1, 600 ml) and the resultingprecipitate is stirred for 30 minutes and collected by filtration. Theprecipitate is redissolved in toluene (80 ml) and the precipitationrepeated in acidic methanol. The precipitate is redissolved inchloroform (80 ml) and passed through a plug of silica, then washedthrough with chloroform (5×100 ml). The combined chloroform phases areconcentrated to ca. 80 ml and precipitated in stirred methanol (600 ml)and stirred for 30 minutes. The polymer is collected by filtration anddried. 0.674 g; 58% recovery of material: M_(W)=650,000, P_(D)=2.21(GPC, PS standards).

The polymerisation protocol in Example 1 may be used to produce eitherhigh M_(W) homopolymers or high M_(W) statistical (random) co-polymersfrom the following monomer families:

A¹ A² A³ A⁴ A⁵ Monomer 2 1 H Br H Br OMe 2,7-dibromo-9,9-dihexylfluorene2 H Br OMe H Br 2,7-dibromo-9,9-dihexylfluorene 3 H Br H H Br2,7-dibromo-9,9-dihexylfluorene 4 H Br H Br OMe 2,7-dibromo-9,9-di(2′-ethylhexyl)fluorene 5 H Br OMe H Br 2,7-dibromo-9,9-di(2′-ethylhexyl)fluorene 6 H Br H H Br 2,7-dibromo-9,9-di(2′-ethylhexyl)fluorene 7 H Br H Br OMe 2,7-dibromo-9,9-diheptylfluorene 8 HBr OMe H Br 2,7-dibromo-9,9-diheptylfluorene 9 H Br H H Br2,7-dibromo-9,9-diheptylfluorene 10 H Br H Br OMe2,7-dibromo-9,9-dioctylfluorene 11 H Br OMe H Br2,7-dibromo-9.9-dioctylfluorene 12 H Br H H Br2,7-dibromo-9,9-dioctylfluorene 13 H Br H Br OMe4,4′-dibromo-2,2′-dihexylbiphenyl 14 H Br OMe H Br4,4′-dibromo-2,2′-dihexylbiphenyl 15 H Br H H Br4,4′-dibromo-2,2′-dihexylbiphenyl 16 H Br H Br OMe1,4-dihexyloxy-2,5-dibromophenyl 17 H Br OMe H Br1,4-dihexyloxy-2,5-dibromophenyl 18 H Br H H Br1,4-dihexyloxy-2,5-dibromophenyl 19 H Br H Br OMe1,4-di(2′-ethylhexyl)oxy- 2,5-dibromophenyl 20 H Br OMe H Br1,4-di(2′-ethylhexyl)oxy- 2,5-dibromophenyl 21 H Br H H Br1,4-di(2′-ethylhexyl)oxy- 2,5-dibromophenyl 22 H Br H Br OMe1,4-dioctyloxy-2,5-dibromophenyl 23 H Br OMe H Br1,4-dioctyloxy-2,5-dibromophenyl 24 H Br H H Br1,4-dioctyloxy-2,5-dibromophenylMonomer 1:

A¹ A² A³ A⁴ A⁵ A⁶ Monomer 2 25 H H H Br OMe Br2,7-dibromo-9,9-dihexylfluorene 26 H H H H Br Br2,7-dibromo-9,9-dihexylfluorene 27 H Br H Br OMe H2,7-dibromo-9,9-dihexylfluorene 28 H Br H H Br H2,7-dibromo-9,9-dihexylfluorene 29 H Br H H Br H2,7-dibromo-9,9-dioctylfluorene 30 H H H Br OMe Br2,7-dibromo-9,9-dioctylfluorene 31 H H H H Br Br2,7-dibromo-9,9-dioctylfluorene 32 H Br H Br OMe H2,7-dibromo-9,9-dioctylfluorene

A¹ A² A³ A⁴ A⁵ A⁷ Monomer 2 33 H Br H H Br H2,7-dibromo-9,9-dihexylfluorene 34 H Br OMe H H Br2,7-dibromo-9,9-dihexylfluorene 35 H Br H H Br H 2,7-dibromo-9,9-di(2′-ethylhexyl)fluorene 36 H Br OMe H H Br 2,7-dibromo-9,9-di(2′-ethylhexyl)fluorene 37 H Br H H Br H 2,7-dibromo-9,9-dioctylfluorene 38H Br OMe H H Br 2,7-dibromo-9,9-dioctytfluorene

Example 2

Monomer 3 (1.0 g, 2.31 mmol) and monomer 4 (2.38 g, 2.31 mmol) aresuspended in toluene (15 ml) and purged by bubbling argon through for 10minutes. Palladium catalyst (1 mol %) is added and the toluene phasepurged for a further 10 minutes. Tetraethylammonium hydroxide (20% aq.solution; 8 ml) is added and the whole heated to reflux for 20 hours.Bromobenzene (0.2 ml) is added and the reaction allowed to proceed for afurther hour, then phenylboronic acid is added and the reaction stirredfor another hour. On cooling the reaction mixture is diluted withtoluene (20 ml) and poured into acidic methanol (10 ml 32% HCl_((aq)) in500 ml methanol) and filtered. The pale solid is redissolved in toluene(100 ml) and stirred vigorously with an aqueous solution of disodiumEDTA (5%, 200 ml) for 1 hour. The toluene phase is separated,concentrated to ca. 50 ml and precipitated in methanol (400 ml),filtered and dried.

The polymerisation in Example 2 may be used to produce eitherhomopolymers or alternating copolymers from the following monomerfamilies:

Monomer 3:

A¹ A² A³ A⁴ A⁵ Monomer 4 39 H Br H Br OMe2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dihexylfluorene40 H Br OMe H Br 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dihexylfluorene 41 H Br H H Br2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dihexylfluorene42 H Br H Br OMe 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di(2′-ethylhexyl) fluorene 43 H Br OMe H Br2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di(2′-ethylhexyl) fluorene 44 H Br H H Br2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di(2′-ethylhexyl) fluorene 45 H Br H Br OMe2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-diheptylfluorene 46 H Br OMe H Br2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-diheptylfluorene 47 H Br H H Br2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-diheptylfluorene 48 H Br H Br OMe2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dioctylfluorene49 H Br OMe H Br 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene 50 H Br H H Br2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dioctylfluorene51 H Br H Br OMe 4,4′-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-dihexylbiphenyl 52 H Br OMe H Br4,4′-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-dihexylbiphenyl 53 H Br H H Br4,4′-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-dihexylbiphenyl 54 H Br H Br OMe1,4-dihexyloxy-2,5-di(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl 55 H Br OMe H Br 1,4-dihexyloxy-2,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl 56 H Br H H Br1,4-dihexyloxy-2,5-di(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl 57 H Br H Br OMe 1,4-di(2′-ethylhexyl)oxy-2,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl 58 H Br OMe H Br1,4-di(2′-ethylhexyl)oxy-2,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl 59 H Br H H Br1,4-di(2′-ethylhexyl)oxy-2,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl 60 H Br H Br OMe1,4-dioctyloxy-2,5-di(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl 61 H Br OMe H Br 1,4-dioctyloxy-2,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl 62 H Br H H Br1,4-dioctyloxy-2,5-di(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl

A¹ A² A³ A⁴ A⁵ A⁶ Monomer 4 63 H H H Br OMe Br2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dihexylfluorene 64 H H H H Br Br 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9- dihexylfluorene 65 H Br H Br OMe H2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dihexylfluorene 66 H Br H H Br H 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9- dihexylfluorene 67 H Br H H Br H2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dioctylfluorene 68 H H H Br OMe Br 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9- dioctylfluorene 69 H H H H Br Br2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dioctylfluorene 70 H Br H Br OMe H 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9- dioctylfluorene

A¹ A² A³ A⁴ A⁵ A⁷ Monomer 4 71 H Br H H Br H2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dihexylfluorene 72 H Br OMe H H Br 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9- dihexylfluorene 73 H Br H H Br H2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-di(2′-ethylhexyl)fluorene 74 H Br OMe H H Br2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-di(2′-ethylhexyl)fluorene 75 H Br H H Br H2,7-di(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-9,9-dioctylfluorene 76 H Br OMe H H Br 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9- dioctylfluorene

Application Example 1

The ITO-glass used for device fabrication is 1 square inch with anominal sheet resistance of 12 ohm/square. The ITO is patterned byphotolithography and etching, then cleaned with water, solvents andfinally by exposure to RF-plasma. The PEDOT-PSS(PEDOT=poly(3,4-ethylenedioxy-thiophene), PSS=poly(styrenesulfonicacid)) layer is spin-coated from aqueous dispersion as acquired fromBayer Corporation and baked at 200° C. for 30 minutes, such that thefinal layer thickness was 40 nm. Polymer 67 is spin-coated from toluenesolution such that the layer thickness is 80 nm. Calcium (20 nm) andaluminium (70 nm) are thermally deposited in a vacuum chamber. Thepatterning of ITO and cathode creates 8 active devices of area 4 mm².

The devices exhibit a turn-on voltage (luminance >1 cd/m²) of 7.4 V,reaching a peak efficiency of 0.012 cd/A.

Example 3

Monomer 5 (1.58 g, 3.18 mmol) and monomer 6 (1.57 g, 3.18 mmol) aredissolved in toluene (22 ml) and purged by bubbling argon through for 10minutes. Palladium catalyst (1 mol %) is added and the toluene phasepurged for a further 10 minutes. Tetraethylammonium hydroxide (20% aq.solution; 12 ml) is added and the whole heated to reflux for 20 hours.Bromobenzene (0.2 ml) is added and the reaction allowed to proceed for afurther hour, then phenylboronic acid is added and the reaction stirredfor another hour. On cooling the reaction mixture is diluted withtoluene (20 ml) and poured into methanol (10 ml 32% HCl_((aq)) in 500 mlmethanol) and filtered. The pale solid is redissolved in toluene (100ml) and stirred vigorously with an aqueous solution of disodium EDTA(5%, 200 ml) for 1 hour. The toluene phase is separated, concentrated toca. 50 ml and precipitated in methanol (400 ml), filtered and dried toyield 1.6 g polymer (85% recovery).

The polymerisation in Example 3 may be used to produce eitherhomopolymers or alternating copolymers from the following monomerfamilies:

A¹ A² A³ Monomer 6 77

H 1,4-dibromo-2,5-bishexyloxybenzene 78

H

1,4-dibromo-2,5-bishexyloxybenzene 79

H 1,4-dibromo-2,5-bisheptyloxybenzene 80

H

1,4-dibromo-2,5-bisheptyloxybenzene 81

H 1,4-dibromo-2,5-bisoctyloxybenzene 82

H

1,4-dibromo-2,5-bisoctyloxybenzene 83

H 2,6-dibromo-1,5-hexyloxynaphthalene 84

H

2,6-dibromo-1,5-bishexyloxynaphthalene 85

H 2,6-dibromo-1,5-bisheptyloxynaphthalene 86

H

2,6-dibromo-1,5-bisheptyloxynaphthalene 87

H 2,6-dibromo-1,5-bisocttyloxynaphthalene 88

H

2,6-dibromo-1,5-bisocttyloxynaphthalene

Application Example 2

The ITO-glass used for device fabrication is 1 square inch with anominal sheet resistance of 12 ohm/square. The ITO is patterned byphotolithography and etching, then cleaned with water, solvents andfinally by exposure to RF-plasma. The PEDOT-PSS layer is spin-coatedfrom aqueous dispersion as acquired from Bayer Corporation and baked at200° C. for 30 minutes, such that the final layer thickness is 100 nm.Polymer 67 is spin-coated from toluene solution such that the layerthickness is 80 nm. Barium (5 nm) and aluminium (100 nm) are thermallydeposited in a vacuum chamber. The patterning of ITO and cathode creates8 active devices of area 4 mm².

The devices exhibit a turn-on voltage (luminance >1 cd/m²) of 3.6 V,reaching a peak efficiency of 0.61 cd/A.

Application Example 3

The ITO-glass used for device fabrication is 1 square inch with anominal sheet resistance of 12 ohm/square. The ITO is patterned byphotolithography and etching, then cleaned with water, solvents andfinally by exposure to RF-plasma. The PEDOT-PSS layer is spin-coatedfrom aqueous dispersion as acquired from Bayer Corporation and baked at200° C. for 30 minutes, such that the final layer thickness is 100 nm.Polymer 67 is spin-coated from toluene solution such that the layerthickness is 80 nm. Lithium fluoride (5 nm), calcium (10 nm) andaluminium (200 nm) are thermally deposited in a vacuum chamber. Thepatterning of ITO and cathode creates 8 active devices of area 4 mm².

The devices exhibit a turn-on voltage (luminance >1 cd/m²) of 3.7 V,reaching a peak efficiency of 1.41 cd/A.

Application Example 4

The ITO-glass used for device fabrication is 1 square inch with anominal sheet resistance of 12 ohm/square. The ITO is patterned byphotolithography and etching, then cleaned with water, solvents andfinally by exposure to RF-plasma. The polyaniline (PANI) layer isspin-coated such that the final layer thickness is 100 nm. Polymer 67 isspin-coated from toluene solution such that the layer thickness is 80nm. Lithium fluoride (5 nm), calcium (10 nm) and aluminium (200 nm) arethermally deposited in a vacuum chamber. The patterning of ITO andcathode creates 8 active devices of area 4 mm².

The devices exhibit a turn-on voltage (luminance >1 cd/m²) of 3.8 V,reaching a peak efficiency of 1.39 cd/A.

1. A co-polymer comprising at least one repeating unit selected from thegroup consisting of

A′ is hydrogen, or C₁-C₁₈alkyl, A² is hydrogen, or C₁-C₁₈alkyl, A³ ishydrogen, or C₁-C₁₈alkoxy, or C₁-C₁₈alkyl, A⁴ is hydrogen, orC₁-C₁₈alkyl, A⁵ is hydrogen, C₁-C₁₈alkyl, di(C₁-C₁₈alkyl)amino, orC₁-C₁₈alkoxy, A⁶ is hydrogen, or C₁-C₁₈alkyl, A⁷ is hydrogen,C₁-C₁₈alkyl or C₁-C₁₈alkoxy, and at least one additional repeating unitT which is selected from the group consisting of

p is an integer from 1 to 10, q is an integer from 1 to 10, s is aninteger from 1 to 10, R¹⁴ and R¹⁵ are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, orC₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, R¹⁶ andR¹⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅aralkyl, or —CO—R²⁸, R¹⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—; R¹⁹ and R²⁰ are independently of each otherC₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁹ and R²⁰ together forma group of formula ═CR¹⁰⁰R¹⁰¹, wherein R¹⁰⁰ and R¹⁰¹ are independentlyof each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by Eand/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, orR¹⁹ and R²⁰ form a ring, which can optionally be substituted, and D is—CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR²⁵—; —SiR³⁰R³¹—; —POR³²—;—CR²³═CR²⁴—; or —C≡C—; and E is —OR²⁹; —SR²⁹; —NR²⁵R²⁶; —COR²⁸; —COOR²⁷;—CONR²⁵R²⁶; —CN; —OCOOR²⁷; or halogen; G is E, or C₁-C₁₈alkyl, whereinR²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; or R²⁵ and R²⁶together form a five or six membered ring, R²⁷ and R²⁸ are independentlyof each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R³⁰ and R³¹ are independently of each otherC₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl, and R³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl.
 2. A co-polymer according to claim 1,wherein T is selected from the group consisting of

R¹⁸ is C₁-C₁₈alkyl, and R¹⁹ and R²⁰ are independently of each otherC₁-C₁₈alkyl which can be interrupted by one or two oxygen atoms, or R¹⁹and R²⁹ form a five or six membered carbocyclic ring, which optionallycan be substituted by C₁-C₄alkyl.
 3. A co-polymer according claim 1,comprising at least one additional repeating unit T in an amount up to99.5 mol %, wherein T is selected from the group consisting of

wherein s is one or two, R¹⁶ and R¹⁷ are independently of each otherC₁-C₁₈alkyl, which can be interrupted by one or two oxygen atoms,C₁-C₁₈alkoxy, which can be interrupted by one or two oxygen atoms andR¹⁹ and R²⁰ are independently of each other C₁-C₁₈alkyl, which can beinterrupted by one or two oxygen atoms.
 4. An optical device or acomponent therefore, comprising a substrate and a polymer according toclaim
 1. 5. An optical device according to claim 4, wherein the opticaldevice comprises an electroluminescent device.
 6. An optical deviceaccording to claim 5, wherein the electroluminescent device comprises(a) a reflective or transmissive anode (b) a reflective or transmissivecathode (c) an emissive layer comprising the polymer located between theelectrodes, and optionally (d) a charge injecting layer for injectingpositive charge carriers, and (e) a charge injecting layer for injectingnegative charge carriers.